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Publication numberUS5245072 A
Publication typeGrant
Application numberUS 07/840,214
Publication dateSep 14, 1993
Filing dateFeb 24, 1992
Priority dateJun 5, 1989
Fee statusLapsed
Publication number07840214, 840214, US 5245072 A, US 5245072A, US-A-5245072, US5245072 A, US5245072A
InventorsThomas J. Giacobbe, George A. Ksenic
Original AssigneeMobil Oil Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for production of biodegradable esters
US 5245072 A
This invention relates to processes for making biodegradable surfactant. The process comprises several steps including an optional step. The first step is directed to reacting olefins with ZSM-23 catalyst to form oligomers having the formula -(C3)x, (C4)x or mixtures thereof. Second, the oligomer is hydroformylated to form a saturated alcohol, for example, tridecanol. Next, the saturated alcohol is ethoxylated. Thereafter a nonionic biodegradable surfactant is recovered. This surfactant can be used in detergent formulations. A process is also taught for making esters which can be used as lubricants or plasticizers. A specific hydroformylation process is taught which utilizes modified cobalt carbonyl catalyst. Also, a specific ethoxylation process is taught. Products formed according to the latter two processes as well as their uses are also taught.
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I claim:
1. A process for the production of biodegradable lubricant ester comprising:
a) contacting C3, C4 olefins, or mixtures thereof, with ZSM-23 catalyst under oligomerization conditions to form oligomers having the formula (C3)x, (C4)x, or mixtures thereof, where x has the value of 1 to 10, said oligomers having an average of 0.8 to 2.0 methyl branches per 12 carbon atoms;
b) contacting step (a) oligomers with hydroformylating catalyst comprising tributyl phosphine modified cobalt carbonyl under hydroformylating conditions comprising temperature between 140 C. and 180 C. and pressure between 200 psig and 1000 psig to form a saturated alcohol containing an average of not more than 2.5 methyl branches per 12 carbon atoms;
c) reacting step (b) saturated alcohol with dicarboxylic acid, under esterification conditions; and
d) recovering a biodegradable lubricant ester having decreased volatility and higher viscosity index compared to isotridecyl alcohol.
2. The process of claim 1 wherein the ester is ditridecyl adipate.
3. The process of claim 1 wherein the ester is ditridecylphthalate.
4. The process of claim 2 wherein said ester has a viscosity index of about 159.
5. A process for the production of plasticizer ester having reduced volatility comprising:
a) contacting C3, C4 olefins, or mixtures thereof, with ZSM-23 catalyst under oligomerization conditions to form oligomers having the formula (C3)x, (C4)x, or mixtures thereof, where x has the value of 1 to 10, said oligomers having an average of 0.8 to 2.0 methyl branches per 12 carbon atoms;
b) contacting step (a) oligomers with hydroformylating catalyst comprising tributyl phosphine modified cobalt carbonyl under hydroformylating conditions comprising temperature between 140 C. and 180 C. and pressure between 200 psig and 1000 psig to form a saturated alcohol containing an average of not more than 2.5 methyl branches per 12 carbon atoms;
c) reacting step (b) saturated alcohol with dicarboxylic acid, under esterification conditions; and
d) recovering a plasticizer ester having decreased volatility.
6. The process of claim 5 wherein said plasticizer ester consists essentially of ditridecylphthalate.
7. The process of claim 5 wherein said plasticizer ester consists essentially of ditridecyladipate.

This application is a divisional application of allowed patent application Ser. No. 07/361,628 filed Jun. 5, 1989, now U.S. Pat. No. 5,112,579, and incorporated herein by reference in its entirety.


The invention relates to a process for preparing surfactants and processes for preparing intermediates used in forming those surfactants. Specifically, the invention relates to the formation of tridecanol, nonionic tridecanol-ethoxylates and anionic tridecanol-ethoxylate sulphates. The invention relates to products formed from the processes as well as uses for the intermediates and surfactant products. The latter product can be used in detergent formulations.


Detergents typically contain surfactant and builder. A high performance builder may contain phosphate, silicate, alkali and antiredeposition agent. See A. Davidsohn, Synthetic Detergents, 7th Edition, Chapter 3, John Wiley & Sons, N.Y. (1987). Builders extend or enhance the surfactant. They soften the water by sequestering calcium and magnesium ions. They inhibit metal corrosion. They make the wash water basic for saponifying glycerides and prevent liberated soil from redepositing on fabric.

Commercially, anionic and nonionic surfactants are most important. Anionic linear alkylbenzene sulfonates (LABS) dominate anionic surfactants. Alcohol-ethoxylates (AE) dominate nonionic surfactants. They have a growing market share. Growth comes from decreasing phosphate use and their superior performance. Phosphate bans, a growing political reality, cause manufacturers to use more surfactant to soften wash water. Moreover, alcohol-ethoxylates remove more sebaceous soil than do linear alkylbenzene sulfonates. They also perform better in both hard and cold water. They formulate more easily into liquid detergents.

Commerical standards have evolved. Dodecylbenzenesulfonic acid sodium salt by Vista Chemical Company and C12-15 alcohol 9-mole-ethoxylate by Shell Chemical Company are among those standards. Manufacture of dodecylbenzenesulfonic acid sodium salt is well documented. Davidsohn, A. S., Milwidsky, B., Synthetic Detergents, 7th Rd., John Wiley, N.Y., 124-127 (1987), hereby incorporated by reference.

NEODOL 25 is a C12-15 linear primary alcohol. See Technical Bulletin SC:84-86 by the Shell Chemical Company. This alcohol is made by a manufacturing process developed by Shell. Surfactants are made from this product. See U.S. Pat. Nos. 3,496,204 and 3,496,203 concerning tertiary organophosphine-cobalt-carbonyl complexes utilized in hydroformulation processes to effect reaction products consisting predominately of primary alcohol by reacting an olefin compound with carbon monoxide in hydrogen at a temperature between about 100 and 300 C. in the presence of the complex. See also U.S. Pat. Nos. 3,440,291; 3,420,898; 3,239,570; 3,239,569; 3,239,566 regarding hydroformylation of olefins. NEODOL 25 has low toxicity. But, undiluted alcohol can be severely irritating to the eye, and on repeated or prolonged dermal contact may be irritating to the skin.

Conventional surfactant synthesis such as that utilized by Shell involves alpha olefin formation based on ethylene as a reactant so that an olefin is formed of the formula (C2)x. That alpha olefin or its internal double bond isomer is subjected to hydroformylation, that is, reaction in the presence of carbon monoxide in hydrogen utilizing a specific catalyst to form an alcohol. That alcohol is ethoxylated in a conventional manner to form an alcoholethoxylate. Thereafter, that compound is sulfonated to form an alcohol-ethoxysulphate. Shell utilizes a catalyst of cobalt in a complex combination with carbon monoxide and a tertiary sixmembered heterocyclic phosphine.

EXXAL 13 is a highly methyl-branched tridecyl-alcohol known for its use in lubricants and detergent formulations which does not require rapid biodegradation.

Applicants have discovered a biodegradable surfactant equal to the commercial surfactants used above. However, applicants' surfactant provides superior economic advantages as well as safety advantages compared to the commercial products.


The invention relates to a process for making biodegradable surfactant comprising a) reacting olefins with ZSM-23 catalyst to form oligomers having the formula (C3)x, (C4)x or mixtures thereof where x has the value of 1 to 10; b) hydroformylating the oligomer to form a saturated alcohol; c) ethoxylating the saturated alcohol; and d) recovering a nonionic biodegradable surfactant.

The invention further relates to a detergent comprising a surfactant selected from a nonionic C10 -C16 alcohol-ethoxylate or an anionic C10 -C16 alcohol-ethoxylate sulphate or alcohol sulfate and salts thereof as well as mixtures thereof.

The invention also relates to a process for making esters comprising reacting olefins with ZSM-23 catalyst to form oligomers having the formula (C3)x or (C4)x or mixtures thereof, where x has the value of 1 to 10, hydroformylating the oligomer and recovering a semi-linear alcohol having less than 1.4 methyl branches whereby the recovered ester has improved low temperature properties, decreased volatility and higher viscosity index compared to isotridecyl alcohol.

The invention relates to a lubricant or plasticizer product comprising a semi-linear alcohol having less than 1.4 methyl branches, having improved low temperature properties, decreased volatility and higher viscosity index compared to isotridecyl alcohol.

The invention further relates to a process for hydroformulation comprising reacting olefins having the formula (C3)x, (C4)x or mixtures thereof, where x has the value of 1 to 10, with a phosphine ligand at a temperature sufficient to promote reaction while retarding paraffin formation.

The invention relates to a surfactant comprising an anionic C10 -C16 alcohol ethoxylate sulphate and salts thereof.


The invention is described using the following figures which are not intended to limit the invention.

FIG. 1 shows yields for tridecanol preparation by hydroformylation with ZSM23-dodecenes;

FIG. 2 shows promotion of CO insertion and alcohol synthesis;

FIG. 3 depicts mechanisms for paraffin formulation.


This invention relates to a process for making biodegradable surfactants for use in detergent formulations. Several steps are required to make the surfactant as well as an optional step. The first step involves reacting olefins with a zeolite catalyst to form oligomers. The second step involves hydroformylating the oligomer. Then, the saturated alcohol formed from that step is ethoxylated. The optional step involves sulphonation of the alcohol ethoxylate formed in the preceding step. These steps will be discussed in seriatim.

ZSM-23 Catalyst

Recent developments in zeolite technology have provided a group of medium pore siliceous materials having similar pore geometry. Prominent among these intermediate pore size zeolites is ZSM-23, which may be synthesized with Bronsted acid active sites by incorporating a tetrahedrally coordinated metal, such as Al, Ga, or Fe, within the zeolitic framework. These medium pore zeolites are favored for acid catalysis. However, the advantages of ZSM-23 structures may be utilized by using highly siliceous materials or cystalline metallosilicate having one or more tetrahedral species having varying degrees of acidity. ZSM-23 crystalline structure is readily recognized by its X-ray diffraction pattern, which is described in U.S. Pat. No. 4,076,842 (Rubin, et al), incorporated by reference.

The shape-selective oligomerization/polymerization catalysts preferred for use herein include the crystalline aluminosilicate zeolites having a silica-to-alumina molar ratio of at least 12, a constraint index of about 8 to 10, and acid cracking activity (alpha value) of about 10-300. A suitable shape selective medium pore catalyst for fixed bed is a small crystal H-ZSM-23 zeolite having alpha value of about 25, with alumina binder in the form of cylindrical extrudates of about 1-5 mm. The preferred catalyst consists essentially of ZSM-23 having a crystallite size of about 0.02 to 2 microns, with framework metal synthesized as gallo-silicate, ferrosilicate, and/or aluminosilicate. These zeolites have a pore size of 4.55.6 Angstroms, such as to freely sorb normal hexane. In addition, the structure must provide constrained access to larger molecules.

It is generally understood that the proportion of internal acid sites relative to external acid sites increases with larger crystal size. However, the smaller crystallites, usually less than 0.1 micron, are preferred for diffusioncontrolled reactions, such as oligomerization, polymerization, etc. Accordingly, it may be required to neutralize more than 15% of the total Bronsted acid sites by chemisorption of a basic deactivating agent.

The degree of steric hindrance should also be considered in the choice of the basic nitrogen compounds, especially the bulky trialkyl pyridine species having alkyl groups of 1 to 4 carbon atoms. Although the selected organonitrogen compound must be bulky enough to prevent infusion of said compound into the internal pores of the catalyst, excessive steric hindrance may prevent effective or complete interaction between the surface Bronsted acid site and the selected basic species.

Catalysts of low surface activity can be obtained by using medium pore, shape selective ZSM-23 zeolites of small crystal size that have been deactivated by one or more trialkyl pyridine compounds, such as 2,4,6-collidine (2,4,6-trimethyl pyridine, gamma-collidine). These compounds all must have a minimum cross-section diameter greater than the effective pore size of the zeolite to be treated; i.e., greater than 5 Angstroms.

When propylene or butene are oligomerized according to processes described herein, a unique mixture of liquid hydrocarbon products are formed. More particularly, this mixture of hydrocarbons may comprise at least 95% by weight of mono-olefin oligomers of the empirical formula:

(Cn H2 n)m 

where n is 3 or 4 and m is an integer from 1 to approximately 10, the mono-olefin oligomers comprising at least 20 percent by weight of olefins having at least 12 carbon atoms, the olefins having at least 12 carbon atoms having an average of from 0.80 to 2.00 methyl side groups per carbon chain, the olefins not having any side groups other than methyl.

It will be understood that methyl side groups are methyl groups which occupy positions other than the terminal positions of the first and last (i.e., alpha and omega) carbon atoms of the longest carbon chain. This longest carbon chain is also referred to herein as the straight backbone chain of the olefin. The average number of methyl side groups for the C12 olefins may comprise any range with the range of 0.80 to 2.00, e.g., from 0.80 to 1.90, e.g., from 0.80 to 1.80, e.g., from 0.80 to 1.70, e.g., from 0.80 to 1.60, e.g., from 0.80 to 1.50, e.g., from 0.80 to 1.40, e.g., from 0.80 to 1.30, etc.

These oligomers may be separated into fractions by conventional distillation separation. When propylene is oligomerized, olefin fractions containing the following numbers of carbon atoms can be obtained: 6, 9, 12, 15, 18 and 21. When butene is oligomerized, olefin fractions containing the following numbers of carbon atoms may be obtained: 8, 12, 16, 0, 24 and 28. It is also possible to oligomerize a mixture of propylene and butene and to obtain a mixture of oligomers having at least 6 carbon atoms.

One use for olefin oligomers described herein, particularly C12 + fractions, is as detergent alcohols. The lower carbon number fractions, particularly C6 -C12, make good intermediates for making plasticizer alcohols. These new olefins could possibly replace linear olefins, the current raw materials for surfactant alcohols and some plasticizer alcohols.

Page and Young (allowed Application Ser. No. 105,438, filed Oct. 7, 1987) described these new olefins as multi-component mixtures of propylene oligomers having relatively few branching methyl groups on the carbon backbone. As an example of branching, the dodecene fraction prepared from propylene and HZSM-23 [ZSM23-dodecenes] typically has 1.3 methyl branches. This can be reduced to 1.0 or less by varying reaction conditions. This compares favorably with dodecenes prepared from propylene and conventional Bronsted or Lewis acids which typically have greater than 3.0 methyl branches. The projected low cost of the ZSM23-olefins, which arises from using a refinery propylene/propane stream as their starting material, makes them economically attractive. Thus, the combination of cost and structure makes ZSM23-olefins possible starting materials for biodegradable surfactant alcohols and high performance plasticizer alcohols.


Hydroformylation, a rhodium or cobalt catalyzed addition of carbon monoxide and hydrogen gas to an olefin, produces aldehydes. See J. Falbe, New Syntheses with Carbon Monoxide, N.Y. (1980); E. J. Wickson, Monohydric Alcohols, ACS Symposium Series 159, Washington, D.C. (1981); Ford, P.C., Catalytic Activation of Carbon Monoxide, ACS Symposium Series 152, Washington, D.C. (1981), all references hereby incorporated by reference. However, Slaugh and Mullineaux discovered that hydroformylations using complexes of tri-nbutylphosphine and cobalt carbonyl catalyze the conversion of olefins directly to alcohols (i.e., the initially formed aldehydes concurrently hydrogenate). Also, the new alcohol function (--CH2 OH) bonds predominately on the carbon chain-end. See Slaugh, L., Mullineaux, R. D., Hydroformylation Catalysts, J. Organomet. Chem.,13, 469-477 (1968); U.S. Pat. Nos. 3,239,569; 3,239,570; 3,329,566; 3,488,158; and 3,488,157, all references hereby incorporated by reference. This permits using a variety of internal olefins as feeds, because they isomerize to a terminal position before hydroformylating. Chain-end hydroformylation maintains alcohol linearity which applicants have discovered is important for making biodegradable surfactants. In contrast, rhodium-based catalysts do not promote olefin isomerization, and hydroformylation occurs predominatly on the original double bond. See Asinger, F., Fell, B., Rupilius, W., Hydroformylation of 1-Olefins in Tertiary Organophosphine-Colbat Hydrocarbonyl Catalyst Systems, Chem. Process Des. Dev., 8(2), 214 (1969); Stefani, A., Consiglio, G., Botteghi, C., Pino, P., Stereochemistry of the Hydroformylation of Olefinic Hydrocarbons with Cobalt and Rhodium Catalysts, J. Amer. Chem. Soc., 99(4), 1058-1063 (1977). The following experiments summarize applicants' effort to prepare tridecanols by hydroformylating ZSM23-dodecenes using tributylphosphine modified cobalt-carbonyl catalyst: ##STR1##


The following examples throughout the remainder of this Specification illustrate embodiments of the invention without limiting it.


Temperature, Pressure, and Catalyst Effects on Tridecanol Yield. Using 2-level factorial designed experiments, applicants hydroformylate ZSM23-dodecenes and measure tridecanol yield while varying temperature (140 to 180 C.), pressure (200 or 1000 psig), and catalyst which is either a mixture of octacarbonyldicobalt and tri-n-butylphosphine or [Co(CO)3 PBu3 ]2. In the factorial design, applicants incorporate both mid-point experiments (160 C., 600 psig, using both catalysts), and subsequently, a star-point experiment (200 C., 1000 psig, using [Co(CO)3 PBu3 ]2 as catalyst). The ZSM23-dodecenes had 1.3 methyl branches on average, a calculated number based on analysis which showed 7% normal dodecenes, 69% monomethyldodecenes, and 24% polymethylated-dodecenes which are assumed to have 2.5 branching methyl groups. Several reaction variables are held constant including mole ratio of hydrogen gas to carbon monoxide at 2:1, dodecene to cobalt mole ratio at 80:1, and use of fresh catalyst for each batch with no recycle. FIG. 1 and Table 1 collect the tridecanol yields which vary from 24 to 70% depending on conditions. The results are

1) Increasing temperature increases yield until leveling off at 180 +/-20 C.

2) Pressure between 200 and 1000 psig of the hydroformylating gas (H2 /CO mixture) has negligible effect on yield.

3) As a hydroformylation catalyst, the physical mixture of [Co(CO)4 ]2 and PBu3 is inferior to [Co(CO)3 PBu3 ]2.

Increasing temperature reportedly accelerates two side reactions, olefin hydrogenation and catalyst decomposition. At 180 +/-20 C., the desired alcohol producing reaction maximizes.

The relatively flat yield response to pressure changes follows the trend Slaugh and Mullineaux observed. The upper and lower faces in FIG. 1 have average yields of 49 and 47%, respectively. However, within this relatively flat yield response, changing pressure causes two small but observable trends. With [Co(CO)4 ]2 and PBu3 as the catalyst precursors, yields decrease (29 to 24% and 50 to 41%) when going to higher pressure. With [Co(CO)3 PBu3 ]2 as catalyst precursor, yields increase (44 to 60% and 63 to 69%) when going to higher pressure. In the former, increasing pressure increases carbon monoxide concentration which presumably pushes equilibria away from [Co(CO)3 PBu3 ]2, the precursor which hydrogenates to active catalyst. In the latter, increasing pressure also increases hydrogen gas concentration which presumably increases hydrogenation of [Co(CO)3 PBu3 ]2 to active catalyst. Thus, depending upon catalyst precursor selection, changing pressure will cause small yield changes.

Compared to [Co(CO)3 PBu3 ]2, the mixture of (Co(CO)4 ]2 and PBu3 is inferior as catalyst. The experiments on the front face of FIG. 1 used the catalyst mixture and have an average yield of 36% compared to 59% for the rear. [Co(CO)3 PBu3 ]2 must be synthesized. Applicants hypothesize that [Co(CO)3 PBu3 ]2 is an intermediate along the path to the active catalyst HCo(CO)3 PBu3, an observable species, and [CO(CO)3 PBu3 ]2 forms in an equilibrium controlled reaction involving [Co(CO)4 ]2, PBu3, and carbon monoxide. See, van Boven, M., Alemdarougiu, N.H., Penninger, J.M.L., Hydroformylation with Cobalt Barbonyl and Cobalt Carbonyl-Tributylphosphine Catalysts, Ind. Eng. Chem. Prod. Res. Develop., 14(4), 259-264 (1975); Whyman, R., In Situ Infrared Spectral Studies on The Cobalt Carbonfl-Catalyzed Hydroformylation of Olefins, 66, C23-C25 (1974), all references hereby incorporated by reference. Thus, the PRESENCE of carbon monoxide inhibits its formation: ##STR2##

Testing that hypothesis, applicants heat a mixture of [Co(CO)4 ]2, PBu3, and ZSM23-dodecenes at 110 C. and atmospheric pressure in the absence of carbon monoxide. Applicants monitor reaction progress by infrared spectroscopy because the firstformed product, the salt (Co(CO)3 (PBu3)2 ]+ [Co(CO)4 ]-, has two intense absorption maxima at 1997 and 1885 cm- 1, and [Co(CO)3 PBu3 ]2 has a single, strong absorption maxima at 1950 cm- 1. See Mirbach, M. F., Mirbach, M. J., Wegman, R. W., Photochemical Ligand Dissociation, Electron Transfer and Metal-Metal Bond Cleavage of Phosphine-Substituted Cobalt Carbonyl Complexes, Organometallics, 3, 900-903 (1984), hereby incorporated by reference. After one hour, the reaction solution contains only [Co(CO)3 PBu3 ]2.

To determine optimal tridecanol synthesis, applicants charge an autoclave with [Co(CO)4 ]2,PBu3, and ZSM23-dodecenes, and heated it at 100 C. and atmospheric pressure for one hour. Then, the autoclave is pressured to 1000 psig with a hydrogen gas-carbon monoxide mixture and heated at 175-180 C. Vacuum distillation (the usual isolation procedure) gave tridecanol in 61% yield. This compares favorably to the 41% yield obtained without pre-reaction heating (compare references 12 and 10 in Table 1), and suggests that this two-component catalyst may give yields approaching 70%, the yield achieved using [Co(CO)3 PBu3 ]2.

Characterization of Tridecanols. The proton-NMR derived branching index, defined as the ratio of integrals for all methyl protons to all protons expressed as a percent, indicates that these tridecanols had 1.4 branching methyl groups, nearly the same number of branching methyl groups in the ZSM23-dodecene feed. See Agrawal, K.M., Joshi, G.C., Microcrystalline Waxes. 1. Investigations on the Structure of Waxes by Proton Nuclear Magnetic Resonance Spectrospocy, 31, 693 (1981), hereby incorporated by reference. This implies that hydroformylation created carbon-carbon bonds on methyl groups only, because no new branches are created. Id. For method to calculate the number of branching methyl groups from the branching index. Table 2 collects physical and spectroscopic data on ZSM23-tridecanol.

Characterization of Recovered C12 's. Not surprisingly, the cobaltcarbonylphosphine catalyst, which readily hydrogenates aldehydes to alcohols, also hydrogenates olefins to undesired paraffins. According to Slaugh and Mullineaux, paraffin formation, which typically averages 10-20%, increases with increasing reaction temperature and olefin branching. In an extreme case, hydroformylation of isobutylene gave 43% of isobutane. Applicants analyzed the recovered C12 fraction from the 70% tridecanol yield hydroformylation (reference 11 in Table 1) looking for olefins and paraffins; this data aids in determining whether tridecanol yield can exceed 70%.

Proton NMR, 13 C NMR, and bromine number determinations establish that the recovered C12 fraction contained greater than 95% paraffin and less than 5% olefin. Two methods, infrared spectroscopy and GLPC analyses, failed. Presumably, this dilute olefin mixture of multiple isomers, each having relatively weak absorbances (C═C stretch, ═C-H bending for tri-substituted olefins), kept the signal buried in the spectra's baseline. GLPC failed because of the mixture's complexity even when starting with a sub-ambient temperature program on a 50 meter capillary column.

The relatively high paraffin yield from these reactions (approx. 25%) indicates that tri-substituted double bonds, or di-substituted olefins that isomerize to trisubstituted olefins, readily hydrogenate. Assuming a methyl group is one of three substituents on these tri-substituted olefins, double bond isomerization toward the methyl carbon and addition of cobalt hydride (the active catalyst) would give an intermediate structurally similar to that formed during hydroformylation of isobutylene. Like isobutylene, the relatively high paraffin content probably results from structural features of these methyl-branched ZSM23-olefins.

Hydroformylating ZSM23-dodecene with phosphine modified cobalt carbonyl catalyst, gives tridecanol in approximately 70% yield. The balance is mostly paraffins formed by olefin hydrogenation.


Instrumentation: Infrared spectra are recorded on a Perkin-Elmer 283 infrared spectrometer using a 3 minute scan. NMR spectra are recorded on a JEOL FX90Q using deuterochloroform as solvent and tetramethylsilane as an internal standard for proton spectra. GLPC is done on a Shimadzu GC-9A fitted with a 50 meter by 0.32 mm ID WCOT fused silica column coated with CP-SL 5CB. Flow rate is 1.8 cm/sec at 0.4 bar inlet pressure. Initial temperature is 60 C. (except for the sub-ambient runs at-15 C.) which is held for 12 min and then heated at 15 C./min until reaching 255 C. where it is maintained for 41 minutes. Injection port is maintained at 300 C. Detector is a FID.

Raw Materials: ZSM23-dodecenes are used as received. The dodecenes having 1.3 methyl branches per C12 consisted of 85% C12, 5% C11 -, and 10% C13 +. The 2:1 volume mixture of hydrogen gas and carbon monoxide are both CP grade. Aldrich Chemical Co. supplied tri-n-butylphosphine. It is used as received and stored under a nitrogen gas atmosphere sealed by a syringe cap. Octacarbonyldicobalt is used as received from Morton Thiokol, Alpha Products Division, and stored in a freezer at 0 F.

General Hydroformylation Procedure: A 300 mL stainless steel pressure reactor (Autoclave Engineers) is fitted with a pressure regulated hydrogen gas-carbon monoxide delivery system and vent with relief valve set at 1500 psig. Reaction temperature is monitored using a thermocouple held in a thermo-well, and maintained using a controller and an electrical heater. The reaction solution is agitated at 300 rpm with a turbine agitator. After flushing the opened autoclave with nitrogen gas, dodecene (84 g, 0.5 mole) and either catalyst A or B is charged. Catalyst A consisted of [Co(CO)3 PBu3 ]2 (8.63 g, 0.0125 mole) and tri-n-butylphosphine (0.6 mL, 0.51 g, 0.0025 mole). Catalyst B consisted of octacarbonyldicobalt (4.28 g, 0.0125 mole) and tri-n-butylphosphine (7.58 mL, 6.06 g, 0.03 mole). In both catalyst A and catalyst B, an excess of tributylphosphine kept the cobalt complexed with phosphine. The excesses are 0.0025 and 0.005 mole for catalyst A and B respectively. The autoclave is sealed and pressure checked with nitrogen gas while agitating. The head-space is charged to 1000 psig with hydrogen gas-carbon monoxide, and then vented to the atmosphere. This is repeated five times to exchange the head-space gases. The reactor contents is heated at the desired temperature until gas consumption ceased; the overall reaction is slightly exothermic. After cooling to room temperature, reactor contents are removed using a pipette.

Isolation of Tridecanol by Batch Distillation: Distillations are done using a glass apparatus consisting of a 2-neck, pear-shaped 100 mL flask, and a 15 cm 150 mm insulated Vigreux column connected to a distillation head which contained a cold finger condenser and pressure equalizing stopcocks for taking fractions during vacuum distillation. Nitrogen gas is slowly bled into the distillation flask through a sub-surface glass capillary tube fitted into one of the two necks. Nitrogen gas flow is adjusted so the vacuum pump could maintain pressure at 0.5+/-0.1 mm Hg. Heat is supplied with a hot air bath constructed from a mantle-heated beaker. Prior to distillation, the crude liquid product is decanted from undissolved catalyst. Distillation of the crude liquid gave paraffins and unreacted dodecenes which are collected from 26 to 85 C. at 0.5 mm Hg. These foamed, but the Vigreux column broke the foam and prevented tridecanol from being carried into this fraction. The Vigreux column is removed after the paraffin/olefin fraction is collected. The fraction boiling from 95 to 140 C. at 0.5 mm Hg, a water-white liquid, is collected, weighed, and labeled as tridecanol. During redistillation, a center cut is collected which boiled at 81-83 C. at 0.15 mm (Hg).

1 H NMR Determination of Branching Index and Branching Methyl Groups: Applicants select the deepest valley occuring near 1.0 ppm, most frequently at 1.1 ppm, and defined methyl protons as those appearing at higher field. Branching Index (BI) is defined as the ratio of integrals for all methyl protons to all protons expressed as a percent. The total number of methyl groups in the molecule are calculated:

Total Methyl Groups=[BI * (n+1)]/150

where n=number of carbon atoms

For the tridecanols, n was taken as 13, and chain ends are defined as methyl and CH2 OH. Thus, the number of branching methyl groups are defined as:

Branching Methyl Groups=Total Methyl Groups-1

Synthesis of [Co(CO)3 PBu3 ]2 : This procedure follows that described by Manning and Forbus, but it contains more details and some minor improvements. See Manning, A. R., Infrared Spectra of Some Derivatives of Octabarbonyldicobalt, (A), 1135-1137 (1968); Forbus, N. P., Kinetics and Mechanisms of Substitution Reactions of Dicolbalt Octacarbonyl, Ph.D. Dissertation, University of Ill., 22-32 (1980), hereby incorporated by reference. With nitrogen gas, purge a 2-neck, 500 mL round-bottom flask fitted with a reflux condenser. While sweeping the flask with nitrogen gas, charge approximately 300 mL of dry toluene. Alternative, evacuate the flask and fill with nitrogen gas. Repeat this 5 times to remove dissolved oxygen gas. Remove the octacarbonyldicobalt from the freezer and allow to warm to room temperature. Quickly weigh in the air octacarbonyldicobalt (34.2 g, 0.1 mole) and charge to the reaction flask while purging with nitrogen gas. Using a syringe, charge tri-n-butylphosphine [49.9 mL (40.4 g), 0.2 mole] into the reaction flask. Heat under reflux for 1 hour. Remove the toluene under reduced pressure, and collect the crude, deep-red [Co(CO)3 PBu3 ]2 by filtration; mp 60-68 C.; mp after recrystallization from toluene 99-102 C. (reported mp 109-111 C.). Store in a tightly sealed gas jar shielded from light.

              TABLE 1______________________________________Reaction Variable Effect on Tridecanol YieldRef- Temper-  Pres-er-  ature    sure    RxTime             Yieldence (C.)         (psig)  (hr)   Catalyst    (%)______________________________________1    140      1000    24     [Co(CO)4]2+PBu3                                    242    140      1000    24     [Co(CO)3PBu3]2                                    603    140       200    48     [Co(CO)4]2+PBu3                                    294    140       200    69     [Co(CO)3PBu3]2                                    445    160       600    42     [Co(CO)3PBu3]2                                    .sup. 64a6    160       600    42     [Co(CO)4]2+PBu3                                    457    180       200    48     [Co(CO)4]2+PBu3                                    508    180       200    48     [Co(CO)3PBu3]2                                    639    180      1000    24     [Co(CO)3PBu3]2                                    6910   180      1000    48     [Co(CO)4]2+PBu3                                    4111   200      1000    48     [Co(CO)3PBu3]2                                    7012   175-180  1000    24     [Co(CO)4]2+PBu3                                    .sup. 61b______________________________________ Notes: a minimum yield due to handling losses during distillation. b heated for one hour at atmospheric pressure in absence of carbon monoxide before adding H2 /CO.

              TABLE 2______________________________________Physical and Spectroscopic Characterization ofZSM23-Tridecanol (1.4 CH3 /C12)______________________________________melting range    -56 to -34 C.density (25 C.)            0.829 g/mLrefractive index 1.4339 at 25 C.elemental analysesa            Calcd for C13 H28 O: C, 77.93;            H, 14.09; O, 7.98.            Found: C, 77.63; H, 13.78boiling point    95-140 C. at 0.5 mm (Hg);            center cut 81-83 C. at            0.15 mm (Hg)viscosity (cSt at 40 C.)            11.59infra-red spectrum            (neat) max, 3300 (O-H), 2900            (C-H), 1460 and 1380            (C-H bending), 1050 cm-1            (C-O)1 H NMR spectrum            (CDCl3) 3.62(t, 1.8H,            J=5.4Hz, CH2 CH2 OH),            2.0-1.1(m, 18.8H, methylene            and methine protons), 1.1-            0.5(m, 7.3H, protons on            methyl groups)______________________________________ Note: a Determined by Schwarzkopf Microanalytical Laboratories, Inc; Woodside, New York.
EXAMPLE 2 Improved Yield Of Tridecanol

Above, applicants made tridecanol, a valuable surfactant intermediate, in 70% yield by hydroformylating dodecene (derived from propylene and HZSM-23 catalyst). This reaction used tributyl phosphine modified cobalt carbonyl catalyst. Here applicants describe improving the tridecanol yield using phenylphosphabicyclononane modified cobalt carbonyl catalyst. Paraffin, formed by olefin hydrogenation, is the major by-product which reduces tridecanol yield. Additionally, applicants wanted to compare alcohol yields using this same catalyst and Shell Chemical olefins, NEODENE 1112 and NEODENE 1314. These olefins are feedstocks to NEODOL 25, a commerical C12-15 detergent alcohol.

Phosphine structure significantly affects hydroformylation including alcohol yield and linearity. See U.S. Pat. 3,420,898; Tucci, E.R., Hydroformylatinc Terminal Olefins, Ind. Eng. Chem. Prod. Res. Dev., 9, 516-520 (1970); Pruett, R. L., Smith, J. A., A Low-Pressure System for Producing Normal Aldehydes by Hydroformylation of Alpha-Olefins, 34(2), 327-330 (1969), hereby incorporated by reference. Highly hindered phosphines, such as 9-phenyl-9-phosphabicyclo[4.2.1]nonane (A), 9-phenyl-9-phosphabicyclo[3.3.1]nonane (B), and 2,2,6,6-tetramethyl-1-phenylphosphorinane (C), give least paraffin and most alcohol. Applicants chose to use phenylphosphabicyclononane, a mixture of A and B. A free radical addition of a phosphine to an olefin gives phenyl-9phosphabicyclononane and similar phosphorus compounds. See Stiles, A. R., Rust, F. F., Vaughn, W. E., The preparation of Organo-Phosphines by the Addition of Phosphine to Unsaturated Compounds, J. Amer. Chem. Soc., 74, 3282-3284 (1952); Rauhut, M. M., Currier, H. A., Semsel, A. M., Wystrach, V. P., The Free Radical Addition of Phosphines to Unsaturated Compounds, 26, 5138-5145 (1961); U.S. Pat. No. 3,401,204; 3,502,730, hereby incorporated by reference. ##STR3##

An improved hydroformylation of ZSM23-dodecene increased tridecanol yield from 70 to 89%. The ZSM23-dodecene came from oligomerizing propylene over HZSM-23 catalyst, and contained 1.3 branching methyl groups. The tridecanol yield equaled the yield from Shell's more linear, internal olefins (Table 4).

              TABLE 4______________________________________Effect of Phosphine Ligand And TemperatureOn Tridecanol YieldsREACTION       ALCOHOL YIELDSCONDITIONS     FEEDS:Temp   Phos-   P/Co    NEODOL  NEODOL  ZSM23-C12C.  phine   ratio   1112    1314    (1.4 CH3)______________________________________180    Bu3P    1.2/1   69      69      69180    A + B   1.2/1   88      89      80135/160  A + B     2/1   85      --      89______________________________________

A combination using mixture A and B as the cobalt catalyst ligand and a relatively low reaction temperature gave the improvement A free radical addition of phenylphosphine to 1,5-cyclooctadiene gave the ligand, a mixture of A and B in a 2 1 ratio (67% Overall yield). ##STR4##

Holding the hydroformylation reaction temperature at 135 C. for 2 hours followed by 160 C. for 48 hours gave ZSM23-tridecanol in 89% yield. The literature teaches that paraffin formation increases with increasing temperature and branching. See U.S. Pat. Nos. 3,329,566; 3,239,569; 3,239,570. Applicants observed that double bonds isomerize more rapidly than hydroformylate. Thus, applicants assume that the three competing reactions have their activation energies ranked as follows:

paraffin formation>hydroformylation>double bond isomerization

Using this assumption, applicants hypothesize that a very low initial temperature (135 C.) mainly isomerizes the double bond to a chain end. This likely distances the double bond from methyl branches. Also, a relatively low hydroformylation temperature (160 C.) reduces undesired paraffin formation The data in Table 4 for ZSM23-dodecene supports this hypothesis. Interestingly, Shell's more linear, internal olefins, NEODENE 1112 and NEODENE 1314, gave highest alcohol yields at 180 C. and at a 1.2:1 phosphorus to cobalt ratio. For comparison, Table 4 also contains tridecanol yields using n-tributyl phosphine as the cobalt ligand. They are inferior to the improved method.

Applicants postulate that increased steric bulk around the cobalt favors more alcohol and less paraffin. Electronic factors however, likely make a small contribution to this change. See Tolman, C. A., Steric Effects of Phosphorus Ligands in Organometallic Chemistry and Homogeneous Catalysis, 77(3), 313-348 (1977); Pruett, R. L., Smith, J. A., A Low-Pressure System for Producing Normal Aldehydes by Hydroformylation of Alpha-Olefins, 34(2), 327-330 (1969), hereby incorporated by reference. Carbon monoxide insertion can occur from a 16 electron intermediate (one vacant bonding site) while an additional CO binds to the acyl-cobalt to maintain 16 valence electrons. Forming the acyl-cobalt relieves steric strain in the 16 electron intermediate by separating the phosphine ligand and olefin moiety (FIG. 2). According to the literature, hydrogenation occurs by either adding hydrogen gas and forming a dihydrido intermediate (path a, FIG. 3) or inserting the cobalt into another cobalt hydride (path b, FIG. 3). The latter path gives a bimetallic cobalt complex. In either path, a congested 18-electron intermediate precedes paraffin formation. This increases hydrogenation activation energy relative to carbonylation, and it results in less paraffin and more alcohol.

Hydroformylation of ZSM23-dodecene gave tridecanol in 89% yield. Using 9-phenyl-9-phosphabicyclononane as the cobalt catalyst ligand and relatively low reaction temperatures increased the alcohol yield by reducing paraffin formation.

Hydroformylation Procedure

The general procedure is described in Example 1. Table 4 contains reaction conditions and reactant and catalyst ratios.

Preparation of 9-Phenyl-9-Phosphabicyclononane

This procedure is a modification of Mason and Van Winkle's. See U.S. Pat. No. 3,400,163. All glassware is dried at 120 C. and assembled hot under a purge of argon. A 250 mL, 3-neck flask is fitted with magnetic spin bar, thermometer, reflux condenser, a rubber syringe septum, argon inlet, and flowmeter. The reactor system is purged overnight with argon flowing at 3 mL/min., and then charged with redistilled 1,5cyclooctadiene [43.3 g (49.1 mL), 0.4 mole, density =0.882 g/mL, from Aldrich Chemical Co.] and phenylphosphine [44.0 g (44.0 mL), 0.4 mole, density =1.00 g/mL, from Strem Chemicals]while under a stream of argon. The reaction solution is heated to 135 C. Di-t-butylperoxide [1.46 g (1.8 mL), 0.01 mole, density=0.796 g/mL, from Aldrich Chemical] is mixed with 5 mL of undecane and added with a syringe pump over 1 hour while maintaining the temperature of the exothermic reaction at 135-145 C. A second portion of di-t-butylperoxide (1.8 mL in 5 mL of undecane) is added rapidly, and the temperature is increased to 150 C. and held for an additional hour. Periodic aliquots, taken with a syringe through the septa, are examined by infrared spectroscopy, and the disappearance of the olefin band at 1645 cm- 1 and the P-H band at 2300 cm- 1 is monitored. After two hours total reaction time, both of these bands had disappeared. The reaction mixture is distilled through a 6-inch Vigreux column and a mixture, 58.3 g (67%) of 9-phenyl-9phosphabicyclo[4.2.1]nonane and 9-phenyl-9phosphabicyclo[3.3.1]nonane, is collected [b.p. 123-125 at 0.1 mmHg], and stored in a refrigerated and septum-sealed flask under a nitrogen gas atmosphere. Reported b.p.: 134-135 C. at 0.3 mm (Hg). Gas chromatography shows the mixture is 67% 9- phenyl-9-phosphabicyclo[4.2.1]nonane (the earlier eluting isomer) and 33% 9-pheny-9-phosphabicyclo[3.3.1]nonane.

EXAMPLE 3 Esters Made From Tridecanol

Applicants synthesized bis-tridecanol esters of adipic and phthalic acid for use as plasticizes and synthetic lubricants. Applicants used two tridecanols, one with relatively low and one with a relatively high degree of methyl branching. The more linear tridecanol came from the hydroformylation of dodecene which originated from propylene using HZSM-23 discussed above. This alcohol contained 1.4 branching methyl groups. Isotridecanol came from Exxon Chemical and contained 3-4 branching methyl groups. The phthalate and adipate made from isotridecanol are Mobil lubricants.

              TABLE 3______________________________________Synthetic Lubricants:Comparison of Tridecyl Phthalates and AdipatesDiisotridecyl-         Ditridecyl-                   Diisotridecyl-                              Ditridecyl-phthalatea         phthalateb                   adipatea                              adipateb______________________________________cSt    83         43.5      26.9     21.240 C.cSt    8.2        6.1       5.3      4.8100 C.Pour   ≦37 C.             -54 C.    -65 C.   -37 C.Point______________________________________ a made from isotridecanol containing 3-4 branching methyl groups b made from tridecanol containing 1.4 branching methyl groups

A 500 mL, 3-neck round bottom flask is equipped with a magnetic stirrer, Dean-Stark water trap, and reflux condenser with a drying tube containing magnesium sulfate. The flask is charged with toluene (250 mL), phthalic anhydride (22.2 g, 0.15 mole), tridecanol (60.11 g, 0.3 mole, containing 1.4 branching methyl groups), and p-toluene sulfonic acid (0.1 g). The reaction is heated under reflux for 20 hours. Three milliliters of water is collected. Removing the solvent under a reduced pressure gave 78.2 g (95%) of ditridecylphthalate, a yellow liquid whose viscosity at 40 C. is 43.5 centistokes.

In comparison, isotridecyl alcohol, which contains 3-4 branching methyl groups, and phthalic anhydride give a product whose viscosity at 40 C. is 83 centistokes. These data show that the more linear alcohol gives a product with improved low temperature properties. Also, one skilled in the art recognizes that more linear alcohols decrease the volatility of esters such as this phthalate. These properties are useful for plasticizing PVC and other plastics. Ditridecylphthalate is also useful as a high temperature lubricant, and finds application in jet engines among other places.

A.250 mL, 3-neck round bottom flask is equipped with a magnetic spin bar, thermometer, rubber septum, nitrogen gas injector, and reflux condenser with exit port. Tridecanol (60.11 g, 0.3 mole, containing 1.4 branching methyl groups) is charged into the flask, and adipoyl chloride (27.45 g, 0.15 mole, purchased from Aldrich Chemical) is added portionwise from a syringe. A slow, continuous nitrogen gas purge swept hydrogen chloride which began to evolve after adding about half the adipoyl chloride. The reaction exothermed to 67 C. After completing the adipoyl chloride addition, the reaction mixture is maintained at 150 C. for 14 hours. The yield is 73.3 g (96%) of a brown liquid. Viscosity at 40 and 100 C. is 21.2 and 4.8 centistokes, respectively (viscosity index=159).

In comparison, isotridecyl alcohol, which contains 3-4 branching methyl groups, and adipoyl chloride gave a product whose viscosity at 40 and 100 C. is 26.9 and 5.3 centistokes, respectively (viscosity index=134). Those skilled in the art generally prefer lubricants with a higher viscosity index.

Table 3 compares the viscometric and pour point data of the four esters. The more linear tridecyl esters are markedly less viscous at 40 C. This demonstrates their excellent low temperature properties, and makes them useful, for example, in maintaining PVC flexibility at ambient and subambient temperatures. The highly branches esters, however, have lower pour points which makes them useful lubricants for engines subjected to very cold temperatures. Ester linearity improves the Viscosity Index (VI), especially of the adipates where VI's of the branched and linear esters are 134 and 159 respectively. Ester linearity also decreases ester volatility and extraction by detergents, two important properties for some plasticizers.

Procedure for Ethoxylating Tridecanols. This procedure follows those by Satkowski and Hsu, and a Shell Chemical Company Bulletin, see Ind. Eng. Chem.; Satkowski, W. B., Hsu, C. G., "Polyoxyethylation of Alcohol", 1957, 49, 1975, and describes synthesizing a tridecanol-ethoxylate containing nine ethylene oxide residues. A 500 mL autoclave is charged with tridecanol [50 g (approximately 60 mL), 0.25 mole] and potassium hydroxide (0.15 g, 0.00268 mole), and heated at 135 C. under vacuum (15 mm Hg or lower) for one hour. This removes water. Nitrogen gas is added until the vessel's pressure is 45 psig. Liquid ethylene oxide [99 g (113 mL), 2.25 mole] is fed on pressure demand from a calibrated, nitrogen gas blanketed Jurgenson gauge which is fitted with a check valve. Ethylene oxide flowed once the reactor's pressure dropped below the pressure of the nitrogen gas blanket. Temperature is maintained at 135-150 C. (exothermic), and pressure kept at less than 100 psig, typically 75 psig. After all the ethylene oxide is added and the pressure approached a steady value, typically 50 psig, the cooled (<60 C.) product is transferred to a nitrogen gas filled bottle that contained sufficient glacial acetic acid (0.161 g, 0.00268 mole) to exactly neutralize the potassium alkoxide catalyst. The product is not purified further, but taken as 100% active material. The product volume (approximately 150 mL) is less than the sum of the reactants because its specific gravity increased to approximately 0.98 g/mL.

Acetylation of Alcohol-Ethoxylates. Applicants followed McClure's procedure which is summarized here. McClure, J. D., Determination of Ethylene Oxide Oligomer Distributions in Alcohol Ethoxylates by HPLC Using a Rotating Disc-Flame Ionization Detector, Presented at the AOCS Meeting, New Orleans, May 1981. Also, Shell Chemical Co. Technical Bulletin SC:580.82. The above-references are hereby incorporated by reference. An acetylation reagent is prepared by slowly adding acetic anhydride (120 mL) with stirring to a solution of p-toluene sulfonic acid monohydrate (14.4 g) and ethyl acetate (360 mL). This reagent is stored in a tightly sealed bottle shielded from light. A 100 mL flask, equipped with a magnetic spin bar and drying tube, is purged with nitrogen gas. Four grams of alcohol-ethoxylate is dissolved in 4 mL of toluene and transferred to the flask along with 12 mL of acetylation reagent. This solution is heated at 50 C. for 30 minutes, transferred to a separatory funnel along with 40 mL of toluene, and washed three times: 100 mL of 30 wt % brine; 100 mL of bicarbonate-brine (50 g sodium bicarbonate, 250 g sodium chloride, 1750 g water); 100 mL of 30 wt % brine. The toluene solution is dried (magnesium sulfate), filtered, and evaporated under reduced pressure giving acetylated alcoholethoxylate, a viscous liquid.

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U.S. Classification560/99, 560/97, 568/909, 560/76, 560/202, 508/496, 524/314, 560/204, 560/190
International ClassificationC10M105/72, C07C41/03, C07C29/16, C11D1/29, C10M105/36, C11D1/72
Cooperative ClassificationC10M105/36, C11D1/72, C10M2207/281, C10M2207/282, C10M2207/34, C11D1/29, C10M2207/283, C10M2219/042, C10M2207/286, C10M2209/104, C10M105/72, C07C29/16
European ClassificationC11D1/72, C10M105/36, C07C29/16, C07C41/03, C11D1/29, C10M105/72
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